Artificial fiber suitable for yielding dyeings fast to fulling



Patented Sept. 10, 1940 UNITED STATES PATENT OFFICE ARTIFICIAL FIBER SUITABLE FOR YIELD- ING DYEINGS FAST TO FULLING Frankfort-on-the-Main, Germany No Drawing. Application September 17, 1937,

Serial No. 164,334. In 1935 Germany November 29,

9ClaimS. (01. 8-22) Our U. S. application Ser. No. 113,012, filed November 27, 1936, relates to artificial fibers suitable for yielding dyeings fast to fulling and process of making same.

Our present invention is a continuation in part of the said application and relates likewise to artificial fibers suitable for yielding dyeings fast to fulling and process of making same.

In employing all types of artificial fibers in admixture with wool, particularly for the manufacture of woven materials which must have an excellent resistance to wear, such as for example military cloth, gentlemens suitings and so on, the tinctorial properties of the artificial fibers involve great difiiculties because they are quite different from those of wool. Hitherto when the material was intended toexhibit particular resistance properties it was necessary to dye the two different fibers by separate dyeing methods. Some other dyeing methods were disadvantageous because the dye-baths could not be exhausted and dyestufi was lost.

Various proposals have already been made for treating the artificial fibers by the addition of such compounds containing nitrogen as are capable of reacting with acid dyestuffs such as for example albu'minous compounds, or for incorporating such compounds into-the fibers. It has been found however, that fibers thus treated canonly be weakly dyed, in particular more weakly than the wool contained in the above mixed textile fabrics. Alternatively, by employing the usual dyeing methods for W001, during the dyeing process at elevated temperatures or during the fulling process the artificial fibers I give up the dyestulf first absorbed to the admixed wool. The latter occurs particularly easily when the fibers have only subsequently been treated with the nitrogenous compounds.

Now we have found that artificial fibers suitable for yielding dyeings fast to fulling' are obtained by incorporating to artificial fibers during their process of manufacture either single or as mixtures nitrogenous bases which contain on the one side an aliphatic radicle of a long chain of carbon atoms, on the other side the chloride and other similar halogenidesd which are fast to boiling. Artificial fibers of the aforesaid kind may be mixed with wool and such mixtures may be dyed according to the single-bath process by means of metachrome dyestufls with the production of equal dyeings, fast to fulling. I I

As nitrogenous base:- which are to be incorporated in the artificial fibers there may be named particularly the condensation product of halogenation products of hard'paraffin (i. e., the well known technical product-of 54 to 56 melting point, consisting of a mixture of saturated hydrocarbons ranging from tetracosan C24H5o to heptacosan Cz'zHss, cf. Ullmann, Enzyklopadie der technischen Chemie, second edition (1912) vol. 2, page 611 ff.) with 'polyalkylene polyamines. As polyalkylene polyamines there may be usedfor the purpose of the present invention particularly the reaction products of ammonia with alkylenc polyhalogenides like ethylene dichloride, ethylene dibromide, propylene dichloride, the halogeno derivatives, of glycerine, butylene dipolyallzylene polyamines thus obtained usually consist of several components of different molecular weight-for example of dialkylene triamines, trialkvlene tetramines and so on. For the present inventionparticularly the crude mixture of these productsmay be used as starting material.

The aforesaid nitrogenous bases may be incorporated single or a plurality thereof, in a given case in admixture with a suitable aliphatic polyamine which has not been subjected to the above condensation reaction.

When the artificial fiber is a viscose material, it is advantageous to employ such material as is similar to copper silk in its properties, for instance an artificial fiber which is obtained by treatment with agents capable of removing water. In some cases it is of an advantage to The subject the fibers before the dyeing process to a cleansing operation using reducing agents such as for example hydrosulfite.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in centigrade degrees. However, we wish it to be understood that our invention is not limited to the particular products nor reaction conditions mentioned therein.

Example 1 YA viscose material whichis prepared by employing a viscose ripened below the usual ripeness is mixed before spinning in a suitable mixfly-- ing vessel for instance in a Werner-Pfleiderer apparatus with 3% of its-weight (with respect to the content of cellulose) of an aqueous suspension of a base obtained by condensing trichloro-hard parafiine with polyethylene-polyamine. (In order to prepare the above trichloroderivative hard parafiine of 54 to 56 C. melting point has been chlorinated by introducing chlorine at temperatures beginning at 80 and ending at 50-60% until an increase in weight corresponding'to the entrance of three chlorine atoms has taken place (cf. U. S. Patent 1,948,- 924). The above polyethylene polyamine mixture has been prepared by acting with aqueous ammonia on ethylene chloride and removing the fractions, boiling under 10 mm. pressure up to 220, by distillation. The residue thus obtained is a viscous brown liquor). The viscose material is spun, acidified, washed and drawn through a hot hydrosulfite bath in order to cleanse it. Then it is washed again and finally treated with alcohol in accordance with the process of our U. S. Patent 2,109,306, February 22, 1938. The fiber thus obtained is distinguished by a woollike appearance. A' textile fabric obtained from the new fiber mixed with wool may be dyed for example with Metachrome Brilliant Blue 8RL (Schultz, Farbstofitabellen, 7th edition, supplement, vol. I, page 111) whereby equal dyeings are obtained, fast to fulling.

Example 2 In a viscose material of the usual degree of ripeness 2% f its weight of the same base as used in Example 1 are incorporated in the above described manner and the viscose is spun in the usual manner. The well washed product is treated at about 50 with a solution of hydrogen peroxide of 1% strength whereby a light fibrous material is obtained, even when a remarkably colored base is used.

A textile fabric obtained from the new fiber may be mixed with wool and dyed for example with Metachrome-olive brown (Schultz, Farbstofftabellen, 7th edition, N0. 142) or Metachromebrown CG (1. 0., vol. 11, page 146) whereby intense and equal dyeings are obtained, entirely fast to fulling. 1

. Example 3 In a viscose material as used in Example 1 immediately while dissolving it or thereafter 4% of its weight of a mixture are incorporated, which consists in the same proportions of the base used in the foregoing examples, of the condensation exhibits a very wool like character and yields,

when dyed according to the meta chrome dyeing process for instance-with Alizarine blue black B (Schultz, l. c. No. 1195) or Chromoxane pure blue (1. 0. vol. II, page 59) dyeings of practically the same fastness to light and fulling as when pure wool has been dyed with the same dyestuffs.

Example 4 A copper-ammonia cellulose spinning solution as usual for spinning copper silk is mixed in a good mixing vessel with 2% ofits weight (related to the cellulose content of the solution) of the condensationproduct as' described in Example 1. Then the solution is shortly deaerated and spun in a spinning funnel into water, soured, cut up and worked up as usual. In a given case to the after-treating bath hydrogen peroxide may be added. In this manner a textile fabric is obtainable whichmay be dyed in admixture with wool with a suitable dyestuff, for instance a metachrome dyestuif, thus yielding dyeings, fast to fulling.

We claim:

1. Artificial fibers prepared from rayon spinning solutions selected from the group consisting of viscose and cuprammonia solutions which fibers contain nitrogenous bases having an aliphatic radic'le ofa long chain of carbon atoms and a-radicle of a polyalkalene polyamine, the fibers being suitable for yielding dyeings fast to fulling.

2. Artificial fibers prepared from rayon spinning solutions selected from the group consistmg of viscose and cuprammonia solutions which fibers contain a condensation product obtained by condensing a tri-chlorinated derivative of hard parafline with a polyethylene polyamine, the fibers being suitable for yielding dyeings fast to fulling.

3. Artificial fibers prepared from a viscose of a low degree ofripeness which fibers contain a condensation product of a tri-chlorinated hard parafiine with a polyethylene polyamine obtained by acting with aqueous ammonia on ethylene dichloride and removing the fractions boiling under mm. pressure up to 220 by distillation, the fibers being suitable for yielding dyeings fast to fulling.

4. Artificial fibers in accordance with claim 1 which are dyed by a metachrome dyestufi.

5. Artificial fibers in accordance with claim 2 dyed with a metachrome dyestufi'.

6. An artificial fiber in accordance with claim 3 dyed with a metachrome dyestufi.

7. Mixed fibers of wool and artificial fibers in accordance with claim 1, which are dyed by means of metachrome dyestuffs with the producttion of equal dyeings, fast to fulling.

8. Mixed fibersof wool and artificial fibers in accordance with claim 2, which are dyed by means of metachrome dyestuffs with the production of equal dyeings fast to fulling.

9. Mixed'fibers of wool and an artificial fiber in accordance with claim 3 which are dyed by means of metachrome dyestuffs with the production of equal dyeings fast to fulling.

ARTHUR voN WEINBERG. HANNS REIN. o'rro 

